Preparation and Characterization of Carbonated Barium Hydroxyapatites

Carbonated barium hydroxyapatite (Ba10(PO4)6(OH)2-2x(CO3)x, X = 0.30-0.57, BaHAP) particles with different Ba/P molar ratios were prepared by a wet method. CO2-3 ions were incorporated into OH- sites of a BaHAP lattice during the preparation at high solution pH. The obtained BaHAP particles were well crystallized and showed a high thermostability. On elevating the mixing temperature of H3PO4 and Ba(OH)2 solutions, the mean particle size of BaHAP particles decreased and their specific surface area increased. The amount of CO2 adsorbed irreversibly on BaHAP particles increased with an increase of their Ba/P molar ratio. Copyright 1999 Academic Press.     

Physicochemical and Sorption Properties of Silica Gel with Immobilized Xylenol Orange Surface Groups

Organomineral sorbents were prepared by sorption immobilization of Xylenol Orange on the surface of two different samples of silica gel from aqueous solutions with pH 1.68 under static conditions. The diffusion coefficients of Xylenol Organe in the near-surface layer of silica gel and the equilibrium sorption constants were determined. Wash-out of the dye from the sorbent was studied. Sorption of Cu(II), Zn(II), and Pb(II) on the sorbents from aqueous solutions with pH 5.8 was studied.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 1, 2005, pp. 73–78.Original Russian Text Copyright © 2005 by Korneev, Kholin.     

Sorption of Copper(II) Ions with Nanosized Magnesium Phosphate

A new approach to the preparation of a nanosized sorbent based on magnesium phosphate has been developed. The patterns of copper(II) ions sorption with nanosized magnesium phosphate from aqueous solutions have been investigated. The sorption parameters have been determined, and the kinetics and mechanism of the processes have been elucidated. The high sorption ability of the nanoscale sorbent has been shown in comparison with existing sorbents based on magnesium phosphate.     

Recovery of heavy metal ions from aqueous solutions using modified organosilicas

Sorption of Cu(II), Pb(II), Cd(II), and Zn(II) from aqueous solutions on two-component organosilicas was studied as influenced by sorbent composition, contact time, ratio of solid and liquid phases, solution pH, nature and concentration of heavy metal ions, and content of modifying agent. The degrees of sorption of these metal ions from aqueous solutions using organosilicas modified with aluminum(III) added into the siloxane matrix or with copper(II) grafted to the sorbent surface layer were compared.     

Removal of heavy metal ions from aqueous solutions using low-cost sorbents obtained from ash

This study’s main objective was the development of effective low-cost sorbents for the removal of heavy metal ions from aqueous solutions. The influence of different factors on the sorption capacity of ash and modified ash as low-cost sorbents obtained by different methods was investigated. The synthesis of new ash-based materials was carried out at ambient temperature (20°C), 70°C, and 90°C, respectively, in an alkaline medium with NaOH concentrations of 2 M and 5 M, respectively, corresponding to a mixture with solid/liquid ratios of 1: 3 and 1: 5, respectively. The prepared materials (sorbents) were characterised by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), X-ray diffraction, and BET surface measurement. Adsorption isotherms were determined using the batch equilibrium method. The results showed that these types of new materials displayed a good capacity to remove copper, nickel, and lead ions (29.97 mg of Cu²⁺ per g of sorbent, 303 mg of Ni²⁺ per g of sorbent, and 1111 mg of Pb²⁺ per g of sorbent) from aqueous solutions. The modified materials were prepared using an alkaline attack (a recognised method used in previous studies), but Romanian ash from a thermal power plant was studied for the above purpose for the first time. Hence, the factors which affect the sorption capacity of the prepared low-cost sorbents were determined and their behaviour was explained, taking into account the composition and structure of the new materials.     

Anilinepropylsilica xerogel used as a selective Cu (II) adsorbent in aqueous solution

The metal ion adsorption properties of the microporous hybrid anilinepropylsilica xerogel were studied using divalent copper, zinc, and cadmium ions in aqueous solutions in concentrations ranging from 10(-4) up to 5x10(-3) moll(-1). At low concentrations the surface of the solid phase presents selectivity for Cu (II), even in competitive conditions. This preferential sorption ability for copper in relation to zinc and cadmium ions was interpreted by considering the xerogel morphology.     

Ion-exchange recovery of palladium(II) from multicomponent chloride solutions

Ion-exchange sorption of palladium(II) from both concentrated aqueous hydrochloric acid solution containing Fe(III), Sn(II), Zn(II), and Cu(II) and weakly acidic concentrated aqueous ammonium chloride solution containing Zn(II) and Cu(II) was studied. The Purolite S920, Purolite S924, and Purolite S984 macroporous resins with the thiourea, thiol, and polyethylenepolyamine functional groups, respectively, were used as sorbents. Strongly basic Purolite A500 anion exchanger was also tested. The desorption of palladium(II) with aqueous ammonia, hydrochloric acid, and acidified aqueous thiourea was examined.     

Sorption of Cobalt on Modified Silica Gel Materials

Various silica gel materials were chemically modified with imidazole, diaza-18-crown-6 (DA18C6) and dibenzod-18-crown-6 (DB18C6). The degree of functionalization of the covalently attached molecule was calculated from C, H, N analysis and ranged between 0.270 and 0.552 mmol/g (for sorbents with imidazole) and between 0.043 and 0.062 mmol/g (for sorbents with DA18C6 and DB18C6). The degree of functionalization depends on the reflux time and silica gel matrix used. Experimental sorption capacity ranged between 0.038 and 0.228 mmol/g (for sorbents with imidazole) and between 0.019 and 0.050 mmol/g (for sorbents with DA18C6 and DB18C6). Synthesized hexagonal mesoporous silica matrix MCM-41 with uniform pore diameter <40 Å was used too. Change of pore diameters of silica gel support to larger pores should have a positive influence on access of cobalt ion to sorption centers to increase of sorption capacity of sorbents. The sorption kinetics of cobalt and the influence of cobalt concentration, pH of various kinds of silica gel matrix with immobilized imidazole group in static conditions on sorption were measured. The sorption of cobalt in various conditions (pH, contact time of phases) with constant liquid-solid ratio (V/m = 50 ml/g) was studied. The distribution coefficients ranged between 200 and 50 000 ml/g (for imidazole), 85 and 120 ml/g (for DB18C6) and between 230 and 500 ml/g (for DA18C6) according to silica gel matrix used and according to the method of sorbent preparation. pH plays important role in the sorption of cobalt on prepared sorbents with immobilized crown ethers due to protonization of crown ethers. Protons significantly competes to sorption of cobalt in acidic solutions. The influence of presence of other heavy or toxic metals (Hg(II), Cd(II), Mn(II), Zn(II), Cu(II), Fe(III), Cr(III), Al(III) and the influence of sodium and potassium on sorption Co(II) from aqueous solutions was investigated. Sorption of cobalt decreases in order Hg > Cu > Cd > Zn, Fe > Mn > Al, Cr. The presence of sodium and potassium ions at concentration 0.05 mol/l significantly influences on the sorption of cobalt with sorbent with immobilized DB18C6 functional group.     

Sorption of cesium on copper hexacyanoferrate/polymer/silica composites in batch and dynamic conditions

The sorption of cesium ions from aqueous solutions on composite sorbents was investigated in static (by the batch method) and dynamic (on column) conditions. The composite sorbents consisted of copper hexacyanoferrate retained by an anion-exchange polymeric layer bound to porous silica beads. The influence of cesium concentration and solution flow rates on cesium sorption were studied. The cesium sorption isotherm obtained is of the Langmuir type. The shape of the breakthrough curves and the sorption capacity for cesium depend on the preparation procedure of the composites.     

Carbon,natural and synthetic sorbents for decontamination of objects of ecosystems from pathogenic microflora

Physico-chemical characteristics and sorption activity of carbon, organosilica sorbents and their modified forms towards proteins, possessing specific activity, and cholerae vibrio have been studied. It was found, that carbon materials modified by copper (II) effectively extracts cholerae vibrio (100%) and may be recommended for disinfection of drinking water. Sorption capacity of organosilica sorbents and their modified by copper (II) forms towards pathogenic microflora (E.coli, St.aureus, Ps.aeruginosa) depending on the composition of the sorbents, concentration of the modified reagent, pH of medium have been evaluated. The rows of the increase of sorption of pathogenic microorganisms by synthetic sorbents in water-salt solutions were established: Al(III)<Zn(II)<Cu (II). It was shown that inhibiting effect of modified synthetic organosilica and natural sorbents towards such pathogenic microorganisms as E-coli, St.aureus Ps.aeruginosa and fungus Bacillus pyocyaneus accordingly is equal 80–98%.     

The enthalpy of interaction between an aqueous solution of methionine and carboxyl cationites in the copper form

The influence of acidity of aqueous solutions of methionine on their interaction with carboxyl cationites in the copper form was studied by the calorimetric, sorption, and spectroscopic methods. The distribution of methionine between aqueous solutions and sorbents with the formation of Cu(II) cation complexes in both phases was observed over the pH range 5–12. The enthalpies of interaction between methionine and KB-2 and Kb-4 cationites in the copper form were determined at various pH.     

Sorption-catalytic determination of cadmium using bromobenzothiazo noncovalently bound to silica and paper

Cadmium (along with Fe(II), Co(II), Zn(II), and Pb(II) ions) decreases the rate of oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) with KIO4 conducted either without or with Mn(II) as a catalyst. Cadmium(II) is preconcentrated from aqueous solutions on silica plates or paper filters physically modified with a reagent for selective determination of Cd(II), namely 1-[(6-bromo-2-benzothiazolyl)azo]-2-naphthol (bromobenzothiazo, or BBT). The modifier is strongly retained on the both supports at pH 6-10 and does not affect the inhibiting effect of Cd(II) in the indicator reaction. Cadmium is determined by its inhibiting action directly on the sorbents by measuring transmittance (BBT/paper) or reflectance (BBT/silica) with limits of detection of 2 x 10(-4) and 0.03 mg/L, respectively. The proposed hybrid combination of sorption with catalytic detection on the sorbent allows to increase the selectivity factors several times (up to 2 orders) relatively to the determination in solution. Tap water samples and soil extracts were analyzed.     

Highly selective ferric ion sorption and exchange by crystalline metal phosphonates constructed from tetraphosphonic acids

With the motivation of searching for highly selective ferric ion sorbents, two open-framework and microporous materials, {[Pb7(HEDTP)2(H2O)] x 7H2O}n (1) and {[Zn2(H4EDTP)] x 2H2O}n (2) [H8EDTP = N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid)], have been synthesized and structurally characterized. The structure of compound 1 results from the seven crystallographically different lead atoms that are bridged by two HEDTP(7-) ligands to yield a three-dimensional microporous framework with tunnels along the a and b axes. Compound 2 features a layer architecture built of square waves along the a axis. The layers are connected by hydrogen bonds between uncoordinated phosphonate oxygen atoms to form a three-dimensional supramolecular network, with one-dimensional tunnels along the a axis. Both compounds 1 and 2 exhibited high ion sorption and exchange capacities for millimolar concentrations of Fe(III). Specifically, when 0.01 g of 1 (or 2) was added to 5 mL of a 1 mM metallic chloride aqueous solution and the mixture was allowed to stand for 2 days at room temperature, compound 1 adsorbed nearly 100% of Fe(III) and compound 2 adsorbed 96.8% of Fe(III). They were also found to adsorb ferric ions selectively over other metal ions, such as Ca(II), Cr(II), Mn(II), Cu(II), Zn(II), Cd(II), etc. Their special ferric ion uptake capacities may be attributed to the cation exchange, coordination bonding, and electrostatic attraction between ferric ions and metal phosphonates.     

Sorption characteristics of chelating resins

Chelating resins are used for preconcentrating metal ions in trace analysis. As part of a systematic study of sorption characteristics of the chelating resin Chelex 100, the sorption of Zn(II) and Cd(II) in different aqueous media was investigated. The distribution coefficient (DC) values for both Zn(II) and Cd(II) were extremely low (<4) in 0.5 to 6M HNO₃ and H₂SO₄ solutions. In HCl solution, theDC values for both Zn(II) and Cd(II) were higher, reaching a peak of nearly 40 in 3M HCl solutions. TheDC values for both Zn(II) and Cd(II) increased with increasing pH in chloride, nitrate, and sulfate solutions (0.1M); the value was nearly 10⁴ for both Zn(II) and Cd(II) between pH 5 and 7 and pH 6 and 8, respectively.     

Study of sorption processes of strontium on the synthetic hydroxyapatite

The sorption of strontium on synthetic hydroxyapatite was investigated using batch method and radiotracer technique. The hydroxyapatite samples were prepared by a wet precipitation process followed by calcination of calcium phosphate that precipitated from aqueous solution. Also, commercial hydroxyapatites were used. The sorption of strontium on hydroxyapatite depended on the method of preparation and it was pH independent ranging from 4 to 9 as a result of buffering properties of hydroxyapatite. The distribution coefficient K _d was significantly decreased with increasing concentration of Sr²⁺ and Ca²⁺ ions in solution with concentration above 1 × 10⁻³ mol dm⁻³. The percentage strontium sorption for commercial and by wet method prepared hydroxyapatite was in the range of 83–96%, while calcined hydroxyapatite was ranging from 10 to 30%. The experimental data for sorption of strontium have been interpreted in the term of Langmuir isotherm. The sorption of Sr²⁺ ions was performed by ion-exchange with Ca²⁺ cations on the crystal surface of hydroxyapatite. Although calcined hydroxyapatite is successfully used as biomaterial for hard tissues repair, it is not used for the treatment of liquid wastes.     

Cadmium removal from single- and multi-metal (Cd + Pb + Zn + Cu) solutions by sorption on hydroxyapatite

Heavy metal contamination of waters and soils is particularly dangerous to the living organisms. Different studies have demonstrated that hydroxyapatite has a high removal capacity for divalent heavy metal ions in contaminated waters and soils. The removal of Cd from aqueous solutions by hydroxyapatite was investigated in batch conditions at 25+/-2 degrees C. Cadmium was applied both as single- or multi-metal (Cd + Pb + Zn + Cu) systems with initial concentrations from 0 to 8 mmol L(-1). The adsorption capacity of hydroxyapatite in single-metal system ranged from 0.058 to 1.681 mmol of Cd/g of hydroxyapatite. In the multi-metal system competitive metal sorption reduced the removal capacity by 63-83% compared to the single-metal system. The sorption of Cd by hydroxyapatite follows the Langmuir model. Cadmium immobilization occurs through a two-step mechanism: rapid surface complexation followed by partial dissolution of hydroxyapatite and ion exchange with Ca resulting in the formation of a cadmium-containing hydroxyapatite.     

Preparation and characterization of carbonated barium-calcium hydroxyapatite solid solutions

Particles of carbonated barium-calcium hydroxyapatite solid solutions (BaCaHap) with different Ba/(Ba+Ca) (X(Ba)) atomic ratios were prepared by a wet method at 100 degrees C and characterized by various means. The crystal phases and structures of the products strongly depended on the composition of the starting solution, that is, the Ba/(Ba+Ca) atomic ratio ([X(Ba)]) and H3PO4 concentration ([H3PO4]) in the solution. BaCaHap with X(Ba)0.43 could be prepared at [X(Ba)]0.7 by changing [H3PO4], but could never be obtained at [X(Ba)]=0.8-0.95 regardless of [H3PO4]. The carbonated calcium hydroxyapatite particles prepared at [X(Ba)]=0 were fine and short rod-shaped particles (ca. 14x84 nm). With increasing [X(Ba)] from 0 to 0.8, the particles obtained became large spherical agglomerates. The carbonated barium hydroxyapatite particles formed at [X(Ba)]=1 were long rod-shaped agglomerates (ca. 0.2x2 microm) of fine primary particles. The amount of CO2 adsorbed irreversibly on a series of BaCaHaps showed a minimum at (Ba+Ca)/(P+C) atomic ratio of around 1.56, which agreed well with the minimum cation/P ratio obtained for the other hydroxyapatites, as already reported.     

Zeolite ZSM-5 containing copper ions: The effect of the copper salt anion and NH<Subscript>4</Subscript>OH/Cu<Superscript>2+</Superscript> ratio on the state of the copper ions and on the reactivity of the zeolite in DeNO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Isotherms of copper cation sorption by H-ZSM-5 zeolite from aqueous and aqueous ammonia solutions of copper acetate, chloride, nitrate, and sulfate are considered in terms of Langmuir’s monomolecular adsorption model. Using UV-Vis diffuse reflectance spectroscopy, IR spectroscopy, and temperatureprogrammed reduction with hydrogen and carbon monoxide, it has been demonstrated that the electronic state of the copper ions is determined by the ion exchange and heat treatment conditions. The state of the copper ions has an effect on the redox properties and reactivity of the Cu-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with propane and in N₂O decomposition. The amount of Cu²⁺ that is sorbed by zeolite H-ZSM-5 from aqueous solution and is stabilized as isolated Cu²⁺ cations in cationexchange sites of the zeolite depends largely on the copper salt anion. The quantity of Cu(II) cations sorbed from aqueous solutions of copper salts of strong acids is smaller than the quantity of the same cations sorbed from the copper acetate solution. When copper chloride or sulfate is used, the zeolite is modified by the chloride or sulfate anion. Because of the presence of these anions, the redox properties and nitrogen oxides removal (DeNO _x ) efficiency of the Cu-ZSM-5 catalysts prepared using the copper salts of strong acids are worse than the same characteristics of the sample prepared using the copper acetate solution. The addition of ammonia to the aqueous solutions of copper salts diminishes the copper salt anion effect on the amount of Cu(II) sorbed from these solutions and hampers the nonspecific sorption of anions on the zeolite surface. As a consequence, the redox and DeNO _x properties of Cu-ZSM-5 depend considerably on the NH₄OH/Cu²⁺ ratio in the solution used in ion exchange. The aqueous ammonia solutions of the copper salts with NH₄OH/Cu²⁺ = 6–10 stabilize, in the Cu-ZSM-5 structure, Cu²⁺ ions bonded with extraframework oxygen, which are more active in DeNO _x than isolated Cu²⁺ ions (which form at NH4OH/Cu2+ = 30) or nanosized CuO particles (which form at NH₄OH/Cu²⁺ = 3).     

Palladium and platinum sorption using chitosan-based hydrogels

Two chitosan hydrogels (prepared by NaOH neutralization and by polyphosphate ionotropic gelation) have been tested in the dry state for Pd(II) and Pt(IV) sorption at pH 2. Similar sorption isotherms with maximum sorption capacities close to 190 mg Pd g⁻¹ and 235 mg Pt g⁻¹ were achieved. The sorption mechanism involves electrostatic attraction of the chloro-anionic species onto protonated amine groups; the drastic decrease of sorption capacity with the addition of chloride ions supports this hypothesis. SEM-EDAX analysis suggests that sorption proceeds, in kinetic terms, through a shrinking core mechanism. Metal ions can diffuse throughout all the sorbent volume. The main differences between the sorbents are revealed by kinetics. The hydrogels prepared by ionotropic gelation in polyphosphate (C-PPh) allows reaching equilibrium much faster than the hydrogels prepared by the neutralization process (C-NaOH). While for C-PPh sorbent the chemical reaction rate seems to control sorption profiles, in the case of C-NaOH a combination of mechanisms including intraparticle diffusion resistance controls uptake kinetics. Metal desorption from loaded sorbents is possible using thiourea alone or in association with HCl solutions. The recycling of the sorbents is possible but for a limited number of cycles.     

Sorption and preconcentration of some heavy metals by 2-mercaptobenzothiazole-clay

2-Mercaptobenzothiazole loaded on previously treated clay was prepared, characterized and used for sorption and preconcentration of Hg(II), Pb(II), Zn(II), Cd(II), Cu(II) and Mn(II) from an aqueous solution. The support used was a natural clay previously treated with sulphuric acid solution. Adsorption isotherms of metal ions from aqueous solutions as function of pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The chemically treated clay was very selective to Hg(II) in solution in which Zn(II), Cd(II), Pb(II), Cu(II) and Mn(II) were also present.